Public GDC Laundry FUN & LSC BS Industrial & Home Care

An Effective Screening Tool for Evaluation of Polymeric Anti-Redeposition Agents and its Correlation with Consumers Visual Perception
G.Nunes*(1), M.Gallotti(1), A.Coimbra(1), A.Lerch(2), R.Morschhaeuser(2) (1)Clariant S.A. (Brazil), (2)Clariant Produkte (Deutschland) GmbH

Global Development Center - Laundry

-!Introduction
-! Historical Background -! Involved Variables -! Types of Soil -! Theory Behind Soil Redeposition -! Anti-Redeposition Additives -! Anti-Redeposition Screening Test -! Anti-Redeposition Methodology -! Comparative Results -! A More Realistic Screening Tool -! Whiteness Maintenance -! Summary & Future Works

Introduction
Soil Redeposition
! Undesirable phenomena ! Responsible for the loss of whiteness

Laundry Detergents Surfactants

! Anti-redeposition effect ! Not enough for laundry ! ! Soil Removal Redeposition Inhibition

Anti-Redeposition Aids
! Many products in the market ! Not easy to generate data to prove their efficiency
An Effective Screening Tool for Evaluation of Polymeric Anti-Redeposition Agents and its Correlation with Consumers Visual Perception Clariant - GDC Laundry FUN & LSC Division BS Industrial & Home Care Slide 2

A new method for anti-redeposition ! Effective, easy and reliable method ! Impact in the final visual perception (stressed and multi-cycle conditions)

-!Introduction

Historical Background
First literary reference to Soap1 2200 BC First multi-component product for laundry, based on soap2 1907 1914 World War I 1918

-! Historical Background
-! Involved Variables -! Types of Soil -! Theory Behind Soil Redeposition -! Anti-Redeposition Additives -! Anti-Redeposition Screening Test -! Anti-Redeposition Methodology -! Comparative Results -! A More Realistic Screening Tool -! Whiteness Maintenance -! Summary & Future Works

1916

Development of the 1st synthetic detergent (Germany)

1932 Patent protecting CMC as anti-redeposition agent (France)3 1936 1939 1946 1945

Multi-component product for laundry based on synthetic surfactant (Europe) 2 World War II

An Effective Screening Tool for Evaluation of Polymeric Anti-Redeposition Agents and its Correlation with Consumers Visual Perception Clariant - GDC Laundry FUN & LSC Division BS Industrial & Home Care Slide 3

Multi-component product for laundry based on synthetic surfactant (USA)2

After WW-II: starts the major concerns about soil redeposition

1.!Soap Technology for the 1990s, Edited by L. Spits American Oil Chemists Society, 1990 2.!Surface Active Agents and Detergents, Vol. II, A.M.Shwartz, J.W.Perry and J.Berch Interscience Publishers, Inc., 1958 3.! Detergency Theory and Test Methods Part I, Surfactant Science Series Vol. 5, Edited by Cutler, W.G. and Davis, R.C. Marcel Dekker Inc., 1972

-!Introduction -! Historical Background

Soil Redeposition: Main Variables Involved

Soil

-! Involved Variables
-! Types of Soil -! Theory Behind Soil Redeposition -! Anti-Redeposition Additives -! Anti-Redeposition Screening Test -! Anti-Redeposition Methodology -! Comparative Results -! A More Realistic Screening Tool -! Whiteness Maintenance -! Summary & Future Works

Surface Tension

Viscosity

Concentration Chemical Composition

Particle Size

Shape

Surface Charge

Substrate

Hardness

Topography

Geometry and nature of the fiber

Eletric charge

Hydrophilicity

Chemical Composition

Detergent
An Effective Screening Tool for Evaluation of Polymeric Anti-Redeposition Agents and its Correlation with Consumers Visual Perception Clariant - GDC Laundry FUN & LSC Division BS Industrial & Home Care Slide 4
-! Detergency Theory and Test Methods Part I, Surfactant Science Series Vol. 5, Edited by Cutler, W.G. and Davis, R.C. Marcel Dekker Inc., 1972

Washing Conditions

Surfactant Concentration

Redepositon Inhibitor

Electrolyte

Time

Water Volume

Mechanical Work

Rinsing Temperature Cond.

-!Introduction -! Historical Background -! Involved Variables

Main Types of Soil

Oily Soil
-!Alters its original shape on deposition and on different systems -!Ex.: Fats and oils from foods and body

-! Types of Soil
-! Theory Behind Soil Redeposition -! Anti-Redeposition Additives -! Anti-Redeposition Screening Test -! Anti-Redeposition Methodology -! Comparative Results -! A More Realistic Screening Tool -! Whiteness Maintenance -! Summary & Future Works

Particulate Soil
-!Retains its original shape on deposition -!Ex.: clay, sand and carbon from the enviroment

An Effective Screening Tool for Evaluation of Polymeric Anti-Redeposition Agents and its Correlation with Consumers Visual Perception Clariant - GDC Laundry FUN & LSC Division BS Industrial & Home Care Slide 5

Particulate + Oily Soil

Colloids and Surfaces A: Physicochemical and Engineering Aspects 74 (1993) 131-167

-!Introduction -! Historical Background -! Involved Variables -! Types of Soil

The Theory Behind Soil Redeposition

The Washing Liquor as a Colloidal System
-- + - -- --- - - -- + --- - -

-! Theory Behind Soil Redeposition

-! Anti-Redeposition Additives -! Anti-Redeposition Screening Test -! Anti-Redeposition Methodology -! Comparative Results -! A More Realistic Screening Tool -! Whiteness Maintenance -! Summary & Future Works

Electrostatic Effect
(charged particles)

Steric Effect
(uncharged particles)
Particle coating with a material that prevents their close approach.

At highly positive or highly negative potentials the particles tend to repel each other forming a stable system.

Average Laundry Conditions

Different Ionic Strengths:
-! Presence of builders, electrolytes and dissolved ions (water hardness).

Material adsorption on the surfaces:

An Effective Screening Tool for Evaluation of Polymeric Anti-Redeposition Agents and its Correlation with Consumers Visual Perception Clariant - GDC Laundry FUN & LSC Division BS Industrial & Home Care Slide 6
Hunter, R.J.;Lee. R. Foundations of Colloid Science Vol. I Oxford Science Publications, Oxford University Press

-! Presence of macromolecules and surfactants that can adsorb on the fabric and/or the particle surfaces.

High Surface Charge:

-! -! High pH values during washing generating highly negatively charged surfaces. Components that increase the charge of the fabric and/or the particle surfaces.

-!Introduction -! Historical Background -! Involved Variables -! Types of Soil -! Theory Behind Soil Redeposition -! Anti-Redeposition Additives -! Anti-Redeposition Screening Test -! Anti-Redeposition Methodology -! Comparative Results -! A More Realistic Screening Tool -! Whiteness Maintenance -! Summary & Future Works

Current Anti-Redeposition Additives

Carboxymethylcellulose
!!Adsorbed on both fabric and particle !!Mainly effective for cotton !!Colloidal stabilizer

Polycarboxylates
!!Adsorption mainly on the fabric !!More effective for polyester fibers !!Polyelectrolyte: eletrosteric effect

Nonionic Polymers
An Effective Screening Tool for Evaluation of Polymeric Anti-Redeposition Agents and its Correlation with Consumers Visual Perception Clariant - GDC Laundry FUN & LSC Division BS Industrial & Home Care Slide 7 Polyvynylpyrrolidone (PVP)
-! Aplicao de CMC em Detergente em P Denver Cotia Ind. E Com. LTDA -!Handbook of Detergents Part A: Properties , Surfactant Science Series Vol. 82, Edited by Broze, G. - Marcel Dekker Inc., 1999 -! Detergency Theory and Test Methods Part I, Surfactant Science Series Vol. 5, Edited by Cutler, W.G. and Davis, R.C. Marcel Dekker Inc., 1972 -! JAOCS 40(11), 699-674 (1963)

!!Adsorbed mainly on soil particles !!Steric effects

Polyvinyl Alcohol (US Patent 3144412)

-!Introduction -! Historical Background -! Involved Variables -! Types of Soil -! Theory Behind Soil Redeposition -! Anti-Redeposition Additives

An Effective Anti-Redeposition Screening Test

!! FLEXIBLE: different needs for each market ! Soil ! Substrate ! Washing Habits ! Formulation !! LOW COST: !! REPRODUCTIBLE ! Equipment ! Raw Materials !! TIME SAVER: ! Availability to test several formulations, soils or substrates at the same time.

-! Anti-Redeposition Screening Test

-! Anti-Redeposition Methodology -! Comparative Results -! A More Realistic Screening Tool -! Whiteness Maintenance -! Summary & Future Works

An Effective Screening Tool for Evaluation of Polymeric Anti-Redeposition Agents and its Correlation with Consumers Visual Perception Clariant - GDC Laundry FUN & LSC Division BS Industrial & Home Care Slide 8

!! RELIABLE !! SIMPLE

-!Introduction -! Historical Background -! Involved Variables -! Types of Soil -! Theory Behind Soil Redeposition -! Anti-Redeposition Additives

The Equipment
Agitation Heating

-! Anti-Redeposition Screening Test

-! Anti-Redeposition Methodology -! Comparative Results -! A More Realistic Screening Tool -! Whiteness Maintenance -! Summary & Future Works

An Effective Screening Tool for Evaluation of Polymeric Anti-Redeposition Agents and its Correlation with Consumers Visual Perception Clariant - GDC Laundry FUN & LSC Division BS Industrial & Home Care Slide 9

Modified Jar Test

Original Jar Test

-!Introduction -! Historical Background -! Involved Variables -! Types of Soil -! Theory Behind Soil Redeposition -! Anti-Redeposition Additives -! Anti-Redeposition Screening Test

The Anti-Redeposition Methodology

Weighting 10g of water Addition of the soil on water

-! Anti-Redeposition Methodology
-! Comparative Results -! A More Realistic Screening -!Tool -! Whiteness Maintenance -! Summary & Future Works

Detergent Solution (3 minutes of stirring)

Addition of the detergent solution solution to the soil solution Dispersion of the soil for 5 minutes

An Effective Screening Tool for Evaluation of Polymeric Anti-Redeposition Agents and its Correlation with Consumers Visual Perception Clariant - GDC Laundry FUN & LSC Division BS Industrial & Home Care Slide 10

Addition of the swatches, one at a time and washing for 30 minutes Rinse one swatch at a time under a slow water flow

-!Introduction -! Historical Background -! Involved Variables -! Types of Soil -! Theory Behind Soil Redeposition -! Anti-Redeposition Additives -! Anti-Redeposition Screening Test -! Anti-Redeposition Methodology -! Comparative Results -! A More Realistic Screening Tool -! Whiteness Maintenance -! Summary & Future Works

Comparative Anti-Redeposition Results

Substrate: Knit 50% CO - 50% PES
Oily Soils
Raw Palm Oil 0.5 g/L Olive Oil / Dye 4.0 g/L

Particulate + Oily Soil

Carbon Black Olive Oil 0.8 g/L

Particulate Soils
ORGANIC Carbon Black 0.5 g/L

INORGANIC Red Clay 3.0 g/L

An Effective Screening Tool for Evaluation of Polymeric Anti-Redeposition Agents and its Correlation with Consumers Visual Perception Clariant - GDC Laundry FUN & LSC Division BS Industrial & Home Care Slide 11

HDP

HDP + Clariant Polymer HDP HDP + Clariant Polymer

HDP

HDP + Clariant Polymer

HDP

HDP + Clariant Polymer HDP HDP + Clariant Polymer

-!Introduction -! Historical Background -! Involved Variables -! Types of Soil -! Theory Behind Soil Redeposition -! Anti-Redeposition Additives -! Anti-Redeposition Screening Test -! Anti-Redeposition Methodology -! Comparative Results -! A More Realistic Screening Tool -! Whiteness Maintenance -! Summary & Future Works

Comparative Anti-Redeposition Results

Substrate: Knit 100% PES
Oily Soils
Raw Palm Oil 0.3 g/L Olive Oil / Dye 2.0 g/L

Particulate + Oily Soil Particulate Soils

ORGANIC Carbon Black 0.5 g/L Carbon Black + Olive Oil 0.5 g/L

INORGANIC Red Clay 3.0 g/L

HDP An Effective Screening Tool for Evaluation of Polymeric Anti-Redeposition Agents and its Correlation with Consumers Visual Perception Clariant - GDC Laundry FUN & LSC Division BS Industrial & Home Care Slide 12

HDP + Clariant Polymer HDP HDP + Clariant Polymer HDP HDP + Clariant Polymer HDP HDP + Clariant Polymer

HDP

HDP + Clariant Polymer

-!Introduction -! Historical Background -! Involved Variables -! Types of Soil -! Theory Behind Soil Redeposition -! Anti-Redeposition Additives -! Anti-Redeposition Screening Test -! Anti-Redeposition Methodology -! Comparative Results -! A More Realistic Screening Tool -! Whiteness Maintenance -! Summary & Future Works

Anti-Redeposition Aids Results

Substrate: Knit 50% CO - 50% PES Carbon Black Olive Oil
Commercial Polycarboxylates
Acrylic / Maleic Acids Copolymer (Avg MW = 70,000) Acrylic Polymer (Avg MW = 4,500)

Clariant Polymer

Commercial CMC
Sodium CMC (degree of substitution = 0.46)

HDP

HDP + Clariant Polymer

An Effective Screening Tool for Evaluation of Polymeric Anti-Redeposition Agents and its Correlation with Consumers Visual Perception Clariant - GDC Laundry FUN & LSC Division BS Industrial & Home Care Slide 13

HDP

HDP + Polycarboxylate

HDP

HDP + Polycarboxylate HDP HDP + CMC

-!Introduction -! Historical Background -! Involved Variables -! Types of Soil -! Theory Behind Soil Redeposition -! Anti-Redeposition Additives -! Anti-Redeposition Screening Test -! Anti-Redeposition Methodology -! Comparative Results

An Even More Realistic Screening Tool

Lower Soil Concentration Multi-Cycle Test Visual Analysis (Panel)

12 evaluators 2 or more tiles with the replicates of each formulation

-! A More Realistic Screening Tool

-! Whiteness Maintenance -! Summary & Future Works

Instructions to organize from the cleanest to the dirtiest Attribution of grades or selection of the best one

An Effective Screening Tool for Evaluation of Polymeric Anti-Redeposition Agents and its Correlation with Consumers Visual Perception Clariant - GDC Laundry FUN & LSC Division BS Industrial & Home Care Slide 14

Statistical treatment of the data

!! Statistical Approach to the Visual Panel: Non-Parametric Analysis -! Paired Comparison: Preference Test -! Multiple Comparison: Friedman-Modified Dan

-!Introduction -! Historical Background -! Involved Variables -! Types of Soil -! Theory Behind Soil Redeposition -! Anti-Redeposition Additives -! Anti-Redeposition Screening Test -! Anti-Redeposition Methodology -! Comparative Results -! A More Realistic Screening Tool

Whiteness Maintenance
Substrate: Knit 50% Cotton 50% Polyester Soil: Carbon Black Olive Oil Soil Concentration: 100 L/L

UV Included

UV Excluded A C B Statistical Approach (UV included and excluded)

-! Whiteness Maintenance
-! Summary & Future Works

AB

Visual Evaluation After 3rd Cycle

Visual Evaluation After 5th Cycle

An Effective Screening Tool for Evaluation of Polymeric Anti-Redeposition Agents and its Correlation with Consumers Visual Perception Clariant - GDC Laundry FUN & LSC Division BS Industrial & Home Care Slide 15

-!Introduction -! Historical Background -! Involved Variables -! Types of Soil -! Theory Behind Soil Redeposition -! Anti-Redeposition Additives -! Anti-Redeposition Screening Test -! Anti-Redeposition Methodology -! Comparative Results -! A More Realistic Screening Tool -! Whiteness Maintenance

Summary & Future Works

!! A new effective and reliable methodology for evaluation of laundry detergents and components has been set up with an extremely simple, however, systematic and meticulous approach. !! As next steps Clariant intend to support customers interested in implementing this methodology. !! As a very active company in the field of laundry applications and polymeric synthesis, Clariant is currently: ! Consolidating a visual panel evaluation ! Concluding works with the screening multi-cycle approach ! Developing new polymeric anti-redeposition additives far more effective them those currently available in the market

-! Summary & Future Works

An Effective Screening Tool for Evaluation of Polymeric Anti-Redeposition Agents and its Correlation with Consumers Visual Perception Clariant - GDC Laundry FUN & LSC Division BS Industrial & Home Care Slide 16

Thank you for your attention

GDC Laundry (So Paulo-BR) Mr. George Nunes george.nunes@clariant.com